Cupriferous trisazo dyestuffs



Patented Sept. 22, 1953 CUPRIFEROUS TRISAZO DYESTUFFS Fritz Kehrer, Basel, Switzerland, assignor to Sandoz A. G., Basel, Switzerland, a Swiss firm No Drawing. Application August '7, 1950, Serial No. 178,174. In Switzerland August 15, 1949 6 Claims. 1

The present invention relates to copper-containing trisazo dyestuffs and to the preparation thereof.

OCH:

It has been found that valuable copper-containing trisazo dyestuffs are obtained by allowing 1 mol of 5,5'-dihydroxy-2,2-dinaphthylamine- 7,7'-disulfonic acid, 1 mol of tetrazotized 3,3'-dimethoxy-4A-diaminodiphenyl, 1 mol of a hydroxynaphthalene-sulfonic acid which corresponds to the formula.

wherein one X is an SOaH group and the other X is a hydrogen atom, Y and Z each stands for an SOaH group or a hydrogen atom, and 1 mol of the diazo compound of an aniline derivative which corresponds to the formula wherein a=H, OCH; or COOH,

b=H. N02. halogen, alkyl or SOaH,

c=H, N02 or SOaH, and

d=H, N02, halogen, alkyl, OCHa, SOaH, SO2NH2.

S0zNH-alky1 or SOzNH-phenyl,

to react with each other in such manner that the 2 new dyestufis are copper complex compounds of the trisazo dyestuffs which correspond to the formula OOH Z O H H O O H a b I Y X H 053 NH S 0 3H d wherein X, Y, Z, a, b, c and d have the afore-indicated significances. The total number of SO3H groups present must be at least four.

More specifically, the new dyestufis can be obtained (1) by coupling the intermediate obtained from 1 mol of tetrazotized 3,3'-dimethoxy-4,4- diaminodiphenyl and 1 mol of a hydroxynaphthalene-sulfonic acid with 1 mol of 5,5-dihydroXy-2,2-dinaphthylamine-7,7-disulfonic acid and then preparing the trisazo dyestuff by adding on 1 mol of a diazotized aniline derivative, or (2) first preparing the monoazo dyestufi from 1 mol of a diazotized aniline derivative and 1 mol of 5,5-dihydroXy-2,2-dinaphthylamine-7,'7 disulfonic acid and then combining this dyestuff with the intermediate obtained from 1 mol of tetrazo tized 3,3'-dimethoxy 4,4 diaminodiphenyl and 1 mol of a hydroxynaphthalene-sulfonic acid, or (3) combining the intermediate obtained from 1 mol of tetrazotized 3,3'-dimethoxy-4,4'-diaminodiphenyl and 1 mol of 5,5'-dihydroxy-2,2'-dinaphthylamine-7,7'-disulf0nic acid with 1 mol of a hydroxynaphthalene-sulfonic acid and coupling the product with a diazotized aniline derivative--and in each case subjecting the obtained trisazo dyestufi to the demethoxylating coppering. This coppering, to produce the copper complex, may be effected by any method wherein the metallization takes place with splitting of the methoxy groups; see for example U. S. Patent No. 2,437,699.

The new dyestuffs dye cotton and regenerated cellulose in brilliant blue shades of very good fastness to light and washing. Compared to the tetrazotized 3,3-dimethoxy-4,4'-dia,minodiphenclosest prior art comparable dyestuff:

yl is attached, on the one hand, to the 2-position (see French patent of Addition No. 20,186 to of the hydroxynaphthalene-sulfonic acid and, on French Patent No. 481,190, Group II, Type XIII,

the other hand, to the 6-position of the 5,5'-dihydroxy-2,2'-dinaphthylamine 7,7 disulfonic acid, and then subjecting the obtained dyestuff to a. demethoxylating coppering. The resultant Example 3, page 22), the dyestufis of the present invention are characterized by superior fastness to Washing and light. The dyestuff of the French patent contains only three sulfonic acid roups in the molecule. Its preparation is characterized by the fact that the conversion of the uncoppered dyestufi" into the copper complex compound is efifcted by means of a conventionalnon-derriethoxylating coppering method. But even if the dyestuff of the French patent is subjected to a demethoxylating coppering, the obtained copper complex is still interior to the new dyestuifs of the present invention. A

The latter contain at leastfour sulfonic acid groups. Notwithstanding the-fact that they are thus of better solubility,th a n the productdescribed in the aforesaid French patent reasition, they are nevertheless unexpectedly characterized by enhanced fastness to washing. Metallization accordingltc the present invention is carried out according to demethoxylating coppering methods, and the resulting. products give dyeings which are faster to light than those of thedyestuff of the'French patent of addition.

Illustrative of naphthol-sulfonic acids which invention, but are not intended to be limitative thereof. The parts are by weight.

Example ,1

24.4 parts of 8,3-dimethoxy-4,4'-diamino-diphenyl are tetrazotized in the usual way and.

.while cooling with ice, are then combined with 33,4, parts of 1 hydroxynaphthalene-3,6,8-trisulionic acid in the presence of sodium carbonate. The obtained intermediate is then coupled with 46.1 parts of -5,5'-dihydroxy-2,2'-dinaphthyl- H 0 8 OH OCHs OCH: OH OH OH HOgS- S0 11 H0 3 NH SO H Cl may be used according to the present invention are 1-hydroxynaphthalene-3-su1fonic acid, l-hydroxynaphthaleneA-sulfonic acid, l-hydroxynaphthalene- 3,8 -disulfonic acid, l-hydroxynaph- ,thaleneJfi-disulfonic acid, l-hydroxynaphthm .lene-lfi-disulfonic acid, l-hydroxynaphthalene- 3,5,8.-trisulionic acid, etc. If use is made, as

couplingcomponent, of a hydroxynaphthalenehydroxybenzene, 6-nitro-4-chloro-2-amino-1- hydroXy-benzene, 6-methyl-4-nitro-2-amino-lhy droxybenzene, G-nitro-4-methyl-2-amino-lhfydroj rybenzene, 5-nitro-4-methyl-2-amino-1- ,hydrogiybenzene, 4,6-dinitro-2 amino 1 hyt aj p tzene. sc a n a s c 4- methoxy 2 amino-benzoic acid, 4-nitro-2- amino 1 hydroxybenzene-S-sulfonic acid, 6-

nitro-Z-amino 1 hydroxybenzene 4 sulfonic acid, Z-amino-1-hydroxybenzene-l-sulfonic acid, 2-amino-l-methoxybenzene-4-sulfonic acid, 4- chloro- 2-ari1ino-l-hydroxybenzene 6 sulfonic acid, S-chlor -Z-amino-l-hydroxybenzene-l-sulionic acid, {l-chloro-Z-ainino-l-hydroxybenzene- 5-su1fonic acid, Z-amino-l-hydroxybenzene-dsulionic acid amide, 2-amino-1-methoxy-4-sulionic acid amide, 2-amino-1-hydroxybenzene-4- sulfonic acid methylamide, 2-amino-l-hydroxybenzenei-sulfonic acid ethylarnide, 2 -amino-lhydroxybenzene-4-sulfonic acid anilide, etc.

The following examples further illustrate the H038 on is converted, in. per se known manner with copper oxide-ammonia solution, into the copper complex compound. However, this conversion may be effected with any other demethoxylating GODP$ri s method. s m en produc bei attained- The copper complex dyescotton and regenerated cellulose in brilliant blue shades of very good fastness to light and washing.

The identical dyestufi is obtained, by first preparing the monoazp dyestufi from 1 mol of the diazo compound from 5-nitro-4-chloro-2-aminol-hydroxybenzene and 1 moi of 5,5-dihydroxy- 2,2-dinaphthylamine-7,'7-disulfonic acid, and then combining this dyestuif wi h the intermediate from 1 mol of tetrazotized 3,3f-dimethoxy- 4,4-diamino-diphenyl and 1 mol of l-hydroxyn hal ec3ia -i ailfe Warewombining the intermediate from 1 mol of tetrazotized 3,3-dimethoxyl,f1'-diamino-diphenyl and 1 moi of 5,5-dihydrOXy-2,2'-dinaphthylamine-7,7disulfonic acid with 1 mol of l-hydi'oxynaphthalone-3,6,8-trisuiionic acid and then coupling with 1 mol of diazotized S-nitro-d-chlorm:l-aniino-lhydroxybenzene, and subjecting the obtained trisazo dyestufl to dcmethoxylating coppering.

Example 2 24.4 parts of 3,3'-dirnethoxy-4,4' dian ino-diphenyl are diazotized in conventional manner and, while cooling with ice, combined with 30.4 parts of 1-hydroxynaphthalene-3,8 disulionic acid in the presence of sodium carbonate. The resultant intermediate is combined, in the presence of excess sodiurncarbonate and of 5-10 vol. pyridine base mixture, with a solution of 66.0 parts of the monoazo dyestuil" from diazotized fi-nitro-4-chloro 2-amino-l-hydroxybenzene and 5,5 dihydroxy-2,2'-dinaphthylamine-7,7'-disulfonic acid, the coupling of which has been effected in a medium alkaline with sodium bicarbonate.

The isolated resultant trisazo dyestuff-which corresponds to the formula OCH:

(i) C H; H O O H H N O 2 H 0 8 NH 5 0 3H 1 6 is converted. in per se known manner with copper Example oxide-ammonia solution, into the copper complex compound. 24.4 parts of 3.3'-dimethoxy-4,4'-diamino- The copper complex dyes cotton and regenerdiphenyl are tetrazotized in the usual manner ated cellulose in brilliant blue shades of very 5 and. while cooling with ice, combined with 38.4 good fastness to light and washing. parts of 1-hydroxynaphthalene-3,6,8-trisulfonic Example 3 acid in the presence of sodium carbonate. The resultant intermediate is coupled, in a medium 24.4 parts of 3,3'-dimethoxy-4,4'-diaminorendered alkaline with sodium carbonate, with diphenyl are tetrazotized in the usual way and. m 46.1 parts of 5,5'-dihydroxy-2,2'-dinaphthylawhile cooling with ice, are combined with 46.1 amine-7,7-disulfonic acid. The thus-obtained parts of 5,5-dihydroxy-2,2'-dinaphthylaminedisazo dyestuif is filtered oil, dissolved in water 7.7-disulfonic acid in the presence of sodium and sodium carbonate, and combined in the presbicarbonate. After formation of the intermedience of 5-10 volume per cent pyridine base mixate, it is coupled-in a medium rendered alkaline ture with the conventionally-prepared diazo comwith sodium carbonate-with 30.4 parts of pound from 16.? parts of 4-methoxy-2-aminol-hydroxynaphthalene-S,B-disulfonic acid. The benzoic acid.

resultant disazo dyestufi is filtered ofi, dissolved The resultant trisazo dyestufi of the formula 1103s on OCH; OCH. HO OH 00011 Ho,s soul BOSS NH son; on,

in water and sodium carbonate, and combined is isolated and converted, in the usual manner in the presence of 5-10 volume per cent pyridine with copper oxide-ammonia solution, into the base mixture with the conventionally-prepared copper complex compound.

diazo compound from 4-nitro-2-amino-1-hy- This copper complex dyes cotton and regenerdroxy-benzene. ated cellulose in brilliant blue shades of very The isolated trisazo dyestuif, which corresponds good fastness to light and washing. to the formula The naphthol-sulfonic acids employed in the H058 OH OCH: OCH; HO OH OH SO3H H058 NH 503B N0;

is then converted, in the usual way with copper preceding examples may be replaced in each case oxide-ammonia solution, into the copper comby, for example, 22.4 parts of l-hydroxynaphplex compound. thalene-3-sulfonic acid, 22.4 parts of l-hydroxy- The copper complex dyes cotton and regenernaphthalene-4-sulfonic acid, or 30.4 parts of ated cellulose in brilliant blue shades of very 1-hydroxynaphthalene-4,8-disulfonic acid, etc., good fastness to light and washing. whereby, while otherwise proceeding as described in the respective examples, dyestufis with similar Example 4 properties are obtained.

24.4 parts of 3.3'-dimethoxy-4,4'-diamino- Similarly, the aniline derivatives employed in dlphenyl are tetrazotized in the conventional the preceding examples may be replaced in each manner and, while cooling with ice, combined case by, for example, 15.7 parts of 4-chloro-2- with 30.4 parts of 1-hydroxynaphthalene-3,6- amino-l-methoxybenzene or 15.4 parts of 5-nidisulfonic acid in the presence of sodium cartro-2-amino-l-hydroxybenzene or 16.8 parts of bonate. The resultant intermediate is coupled, 6-methyl-4-nitro-2-amino-l-hydroxybenzene or in a medium rendered alkaline with sodium 16.8 parts of 6-nitro-4-methyl-2-amino-1-hycarbonate, with 46.1 parts of 5,5'-dihydroxydroxy-benzene or 16.8 parts of 5-nitro-4-methyl- 2,2-dinaphthylamine-'l,7-disulfonic acid. The E 2-amino-l-hydroxybenzene or 19.9 parts of 4,6- thus-prepared disazo dyestuff is filtered off. disdinitro-2-amino-l-hydroxybenzene or 18.2 parts solved in water and sodium carbonate, and comof 5-nitro2-amino-benzoic acid or 23.4 parts of bined in the presence of 5-10 volume per cent 6 nitro 2 amino 1 hydroxybenzene 4 pyridine base mixture with the conventionallysulfonic acid or 18.9 parts of 2-amino-l-hydroxyprepared diazo compound from 23.4 parts of 4 nitro 2 amino 1 hydroxybenzene 6 benzene-4-sulfonic acid or 20.3 parts of 2-amino- 1-methoxybenzene-4-sulfonic acid or 22.3 parts sulfonic acid. of 4-chloro-2-amino-l-hydroxybenzene-6-sul- The resultant trisazo dyestufi of the formula ionic acid or 22.3 parts of 6-chloro-2-amino-1- on OCH; 00H. HO OH no so r:

N=N N=N N=N noassoap H038 NH- S0;H No,

is isolated and converted, in the usual manner hydroxybenzene-4-sulfonic acid or 22.3 parts of with copper oxide-ammonia solution, into the 4 chloro 2 amino 1 hydroxybenzene 5 copper complex compound. sulfonic acid or 18.8 parts of 2-amino-1-hydroxy- The copper complex dyes cotton and regenerbenzene-4-sulfonic acid amide or 20.2 parts of ated cellulose in brilliant blue shades of very 2 amino 1 methoxybenzene 4 sulfonic acid good fastness to light and washing. amide or 20.2 parts of 2-am1n0-1-hydroxybenzene-4-sulfonic acid ,methylamide or 21.6 parts of 2-amino-1-hydroxybenzene-4-suli?onic acid ethylamidei or 26.4 partsof 2eamino-l-hydroxybenzene-sulfonic acid aniline, etc., -whereby, while otherwise proceeding as (described in'the respective examples,'.dyest1ifis withisiniilar properties are Obtained.

Both the naphthol-sulfonic acids and the H035 59H 'OCHa 00H:

H 0 (I) H 0 H H0 58 NH S 0311 l oaH 3. The copper complex of the trisazo dye'stuff of the formula O OH H0 33- NH- S 0 3H 1 ternatives above-enumerated and while other- 4. The copper complex of the trisazo dyestuff wise proceeding as described in the examples, and of the formula mots OH 00113 OOH: (5H

-SO3'H N01 H 0 8- NH* 5. The copper complex of the trisazo dyestuff from the group consisting of hydrogen, N02 and SOrI-I, and d stands for a member seleotdf-rom the group consisting-of hydrogenfiNoz; halogen, lower alkyl, OCHs, SOsH, SO2NH2, SOzNH-lower alkyl and SOZNH-phenyI, andwherein the total number of SOaH groupsis at least four.

2. The copper complex of the trisazo dyestufi of the formula aniline derivativesemployed inthe precedingexamples maybe replaced by. theoorresponding alobtained. of the formula on OCH; OCH; HO OH HO soZH no. SO=H HO;S NH SO3H N01 6. The copper complex of the trisazo dyestuff of the formula OCH:

1. A copper complex compound of a trisazo dyestufi of the formula Z .03 "Cl)CH| OCH; HO 0H 11 b HO NH- --SO;H d

FRITZ KEHRER.

Having thus 'd'isclosed the invention what is claimed is:

HO;S 011 C O OH HO;S SO-sH C Hg wherein one Xstands for SOaH andthe other X for hydrogen, Y and 'Z -each stands-tor amem- References Cited in the file of this patent ber selected fromthe group-consisting ofSOfiH 60 UNITED STATES PATENTS and hydrogen, a stands for a member selected from the group consistingof OH,'OOH3, and Nqmbel .Name Date COOH, bstands for a memberselectedfromthe Ulrich et Sept 1892 group consisting of hydrogen, N02, halogen. lower 65 23: 1: et a1 1 1 and so H, c stands for a member selected e 3 2,459,467 Straub et a1 Jan. 18, 1949 FOREIGN PATENTS "Number Country Date 7 481,190 France Aug. 19, 1916 20,186 France Oct. 3, 1916 1st addition to No. 481,190 

3. THE COPPER COMPLEX OF THE TRISAZO DYESTUFF OF THE FORMULA 